CN105238092A - Novel 2,6-site-substituted BODIPY organic dye sensitizer and preparation method therefor - Google Patents

Novel 2,6-site-substituted BODIPY organic dye sensitizer and preparation method therefor Download PDF

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CN105238092A
CN105238092A CN201510734235.8A CN201510734235A CN105238092A CN 105238092 A CN105238092 A CN 105238092A CN 201510734235 A CN201510734235 A CN 201510734235A CN 105238092 A CN105238092 A CN 105238092A
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CN105238092B (en
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赵鸿斌
周伟男
彭敏
张文涛
廖俊旭
宗乔
徐晓林
谢泽川
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Pizhou Runhong Industry Co.,Ltd.
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Dongguan University of Technology
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells

Abstract

The present invention relates to a novel 2,6-site-substituted BODIPY organic dye sensitizer and a preparation method therefor. The organic dye sensitizer is organic photovoltaic materials with a D-pi-A structure. By taking a meso-site-substituted BODIPY core as a pi bridge framework, the sites 2 and 6 of the BODIPY core is respectively substituted by an electron donor and an electron acceptor. The present invention further discloses a preparation method for the above the dye sensitizer. The preparation method obtains a dye molecule having a general structural formula I by taking 2,4-dimethylpyrrole as an initial reaction raw material, performing a serials of simple synthesis reactions, and finally performing classical Suzuki coupling and Knoevenagel condensation reactions. The dye sensitizer synthesis method is simple, easy to control and high in yield, and has general applicability. When the method is applied to dye sensitized solar cell preparation, a dye sensitized solar cell material with a high fill factor and an ideal photoelectric conversion efficiency can be obtained. The formula I is shown in the description.

Description

Organic dye sensitized dose of BODIPY class that a kind of novel 2,6-positions replace and preparation method thereof
Technical field:
The present invention relates to dye sensitization solar battery Material Field, organic dye sensitized dose of the BODIPY class of particularly novel 2, the 6-positions replacements of one.
Background technology:
From Switzerland in 1991 group adopts bipyridyl ruthenium as dyestuff and nanoporous TiO first 2since film preparation dye sensitization solar battery (DSSCs), dye sensitized nano crystal TiO 2solar cell becomes with regard to relying on low preparation cost and higher photoelectric transformation efficiency the study hotspot that recent two decades comes solar energy photoelectric conversion field.Light-sensitive coloring agent mainly comprises metal complexes and pure organic dye.At present, the metal complexes based on [Ru(bpy)2(dppzi), because of its good stability and higher effciency of energy transfer, obtains extensive and deep research.But ruthenium dye exists as resource-constrained, the inferior position such as expensive, which has limited its application.Compared with ruthenium dye, pure organic dye, because of advantages such as its low raw-material cost, structure design flexible, easy synthesis, easily purifications, has become the popular direction that current DSSCs studies.
Fluorine boron complexing two pyrroles (BODIPY) derivative is the good light-sensitive coloring agent of a class, has satisfactory stability, molar extinction coefficient (1 × 10 that modifiability is good, high 5m -1cm -1) and higher oxidizing potential, it is applied to dye sensitization solar battery and has bibliographical information.The spectral absorption relative narrower of BODIPY, but its good modifiability can overcome this shortcoming, realizes the red shift of spectral absorption and widens, and is conducive to the Jsc improving battery, has shown good application prospect.Carbazole derivative is the another kind of compound with good photoelectric property.It has strong spectral absorption and emission characteristic, very high cavity transmission ability and wider band gap, is widely used in field of photovoltaic materials.In view of the photoelectric property that two class materials are outstanding, therefore, BODIPY is combined with carbazole compound, be applied to the research interest that dye sensitization solar battery causes us.
Design and synthesis of the present invention one class BODIPY2, the novel D-π-A dye sensitizing agent that 6-position is given respectively, replace by body unit, and the synthetic method of such dyestuff is optimized, improve such BODIPY Dyestuff synthesis productive rate, effectively improve the photovoltaic performance of such BODIPY dyestuff.
Summary of the invention:
The object of this invention is to provide organic dye sensitized dose of the BODIPY class that a kind of novel 2,6-positions replace, it has novel molecular structure, has lower edge energy, wide spectral absorption scope
Another object of the present invention is to provide the preparation method of such dye sensitizing agent, and the method reaction conditions is easy to control, and product purification is simple, and productive rate is higher, and has universality.
For achieving the above object, the present invention is by the following technical solutions:
Organic dye sensitized dose of the BODIPY class that a kind of novel 2,6-positions replace, has the chemical structure of general formula I:
In formula I, D is donor monomer, the one in following structural unit:
Wherein, R 1for H or alkyl or alkoxyl group;
A is by body unit, the one in following structural unit:
The preparation method of organic dye sensitized dose of the BODIPY class that a kind of novel 2,6-positions replace, comprises the following steps:
(1) by 2,4-dimethyl pyrrole and acyl chlorides generation condensation reaction, then carry out complex reaction with boron trifluoride diethyl etherate, obtained intermediate 1, its structure is:
(2) intermediate 1 is through dimension David Smail formylation reaction, and obtain intermediate 2, its structure is:
(3) intermediate 2 and iodine monochloride are through electrophilic substitution reaction, obtained intermediate 3, and its structure is:
(4) carbazole and n-octane bromide are reacted under the effect of alkali, obtained intermediate 4, its structure is:
(5) intermediate 4 and N-bromo-succinimide at room temperature react, and obtain intermediate 5, its structure is:
(6) intermediate 5 and duplex tetramethyl ethylene ketone boron ester are under the catalysis of catalyzer, and through Suzuki linked reaction, obtain intermediate 6, its structure is:
(7) 2-bromine carbazole and n-octane bromide react under the effect of alkali, obtained intermediate 7, and its structure is:
(8) intermediate 7 and duplex tetramethyl ethylene ketone boric acid ester are under the catalysis of catalyzer, and through Suzuki linked reaction, obtain intermediate 8, its structure is:
(9) by paraiodoanisole and carbazole under the catalysis of catalyzer, through Liv Ullmann condensation reaction, obtained intermediate 10, its structure is:
(10) intermediate 9 and N-bromo-succinimide are reacted, obtain intermediate 9, its structure is:
(11) by paraiodoanisole and 2-bromine carbazole under the catalysis of catalyzer, through Liv Ullmann condensation reaction, obtained intermediate 11, its structure is:
(12) by intermediate 10 with duplex tetramethyl ethylene ketone boric acid ester under the catalysis of catalyzer, through Suzuki linked reaction, obtained intermediate 12, its structure is:
(13) by intermediate 11 with duplex tetramethyl ethylene ketone boric acid ester under the catalysis of catalyzer, through Suzuki linked reaction, obtained intermediate 13, its structure is:
(14) by 4-(9H-carbazole-9-base) phenylo boric acid and intermediate 3 under the catalysis of catalyzer, through Suzuki linked reaction, obtained intermediate 14, its structure is:
(15) respectively by intermediate 6,8,12,13 and intermediate 3 under the catalysis of catalyzer, through Suzuki linked reaction, obtained intermediate 15,16,17,18, its structure is:
(16) intermediate 14 ~ 18 respectively with cyanoacetic acid through Knoevenagel condensation reaction, obtained target dye molecule Dye1-5, its structure is:
Preferred as technique scheme, in step (1)-(15), the reaction medium of described reaction is one or more mixing of DMF, piperidines, tetrahydrofuran (THF), normal hexane, methylene dichloride, ethyl acetate, toluene, chloroform, ethanol.
Preferred as technique scheme, in step (6), (8), (10), (11), (12), (13), (14), (15), described catalyzer is Pd (PPh 3) 4, Pd (dppf) Cl 2, one in CuI.
Preferred as technique scheme, temperature of reaction in described step (2), (6), (8), (9), (11), (12), (13), (14), (15), (16) is 75-120 DEG C, and the reaction times of step (1)-(15) is 5-48h.
Compared with prior art, the present invention has following beneficial effect:
(1) in synthetic method, the method raw material is common to be easy to get, and production cost is low, and reaction conditions is more easy to control, and purifying products is simple, have universality, and the yield of product improves greatly;
(2) by the spectral data analysis to dyestuff, we can find out that such dyestuff has good photon capture ability, dyestuff compared to bibliographical information has wide uv-absorbing scope, is applied to dye sensitization solar battery, has high photovoltage and packing factor.
Accompanying drawing illustrates:
Fig. 1 is the nucleus magnetic hydrogen spectrum of Dye1.
Fig. 2 is the nuclear-magnetism carbon spectrum of Dye1.
Fig. 3 is the nucleus magnetic hydrogen spectrum of Dye2.
Fig. 4 is the nuclear-magnetism carbon spectrum of Dye2.
Fig. 5 is the nucleus magnetic hydrogen spectrum of Dye3.
Fig. 6 is the nuclear-magnetism carbon spectrum of Dye3.
Fig. 7 is the nucleus magnetic hydrogen spectrum of Dye4.
Fig. 8 is the nuclear-magnetism carbon spectrum of Dye4.
Fig. 9 is the nucleus magnetic hydrogen spectrum of Dye5.
Figure 10 is the nuclear-magnetism carbon spectrum of Dye5.
Figure 11 is the ultra-violet absorption spectrum of Dye1-5 in dichloromethane solution.
Figure 12 is the cyclic voltammetry curve of Dye1-5 in dichloromethane solution.
Figure 13 is the I-V curve that Dye1-5 prepares organic dye sensitized solar cell.
Embodiment:
For a better understanding of the present invention, below by embodiment, the present invention is further described, and embodiment, only for explaining the present invention, can not form any restriction to the present invention.
(1) synthesis of intermediate 1
In the there-necked flask of 250mL, add 2,4-dimethyl pyrrole (3.3g, 35mmol) and new steaming methylene dichloride 40mL, load onto reflux condensing tube.Vacuumize, argon shield.Positive caproyl chloride (2.5mL, 18mmol) is dropwise added, mixed solution reflux 3h with syringe.Be cooled to room temperature, normal hexane dilutes, and stirring is spent the night, removal of solvent under reduced pressure.Add new steaming toluene 80mL, stir, add triethylamine (15mL, 113mmol), after 20min, dropwise add boron trifluoride diethyl etherate (20mL, 163mmol), continue room temperature reaction 1h, reaction mixture is through removing solvent under reduced pressure, dichloromethane solution dilutes, saturated common salt washing (3 × 50mL), anhydrous magnesium sulfate drying.Crude on silica gel column chromatography obtains red brown solid. 1HNMR(400MHz,CDCl 3)δ6.05(s,1H),2.96–2.90(m,1H),2.51(s,3H),2.41(s,3H),1.62(d,J＝6.6Hz,1H),1.46(d,J＝6.8Hz,1H),1.42–1.35(m,1H),0.93(t,J＝6.7Hz,2H). 13CNMR(101MHz,CDCl 3)δ:153.70,146.74,140.32,131.45,121.55,32.59,31.65,28.46,22.53,16.36,14.47,14.45,14.42,14.06.
(2) synthesis of intermediate 2
In the there-necked flask of 100mL, add 10mLN, dinethylformamide, vacuumize, logical argon shield, by reaction flask as in ice-water bath, slowly drips POCl 3(6.5mL, 7.00mmol), 5min drips off, and reaction flask is placed in room temperature reaction 30min.0.524g intermediate 1 is dissolved in 30mL1,2-ethylene dichloride, after dripping, is warming up to 50 DEG C of reaction 2h.Be cooled to room temperature, reaction solution is slowly poured in unsaturated carbonate potassium solution.Dichloromethane solution extracts, and organic phase washes 3 times, anhydrous magnesium sulfate drying.Thick product obtains yellow solid through silica gel column chromatography. 1HNMR(400MHz,CDCl 3)δ:10.05(s,1H),6.18(s,1H),3.03–2.93(m,2H),2.72(s,3H),2.69(s,3H),2.52(s,3H),2.43(s,3H),1.48(s,2H),1.44(d,J＝6.7Hz,2H),1.39–1.34(m,2H),0.89(t,J＝6.9Hz,3H).
(3) synthesis of intermediate 3
Intermediate 2 (226mg, 0.6mmol), 20mL methyl alcohol/DMF (V/V=1:1) is added in 50mL there-necked flask.Vacuumize, under argon shield, slowly drip the methanol solution of iodine monochloride.Under room temperature, continue to stir half an hour, TLC detects that raw material total overall reaction is complete.Add 20mL water in reaction flask, dichloromethane extraction 3 × 30mL, merge organic phase, organic phase saturated sodium thiosulfate solution washes 3 times.Organic phase anhydrous magnesium sulfate drying, crude on silica gel column chromatography obtains red solid, productive rate 65%. 1HNMR(400MHz,CDCl 3)δ:10.13(s,1H),3.08(d,J＝7.1Hz,2H),2.79(s,3H),2.77(s,3H),2.67(s,3H),2.54(s,3H),1.71–1.61(m,2H),1.51(d,J＝7.6Hz,2H),1.41(dd,J＝14.0,7.1Hz,2H),0.95(t,J＝7.0Hz,3H). 13CNMR(101MHz,CDCl 3)δ:186.06,159.10,156.79,149.26,144.90,141.91,133.66,130.14,126.54,32.45,31.48,29.15,22.50,19.40,16.48,14.02,13.18,12.88.
(4) synthesis of intermediate 4 (9-octylcarbazol)
In 250mL there-necked flask, add 5g (15.4mmol) carbazole successively, 100mLDMSO, 0.25g (1.1mmol) TEBA and 25mL sodium hydroxide solution (50wt%), in 0.5h, (3.3g is dripped under magnetic agitation, 16.9mmol) 1-bromine octane, room temperature reaction 8h, stopped reaction, add hydrochloric acid in reaction solution and regulate PH=7, be extracted with ethyl acetate (3 × 50mL), merge organic layer and use saturated common salt water washing 3 times, anhydrous magnesium sulfate drying spends the night, distilling off solvent after filtering, residuum sherwood oil is eluent column chromatography for separation, obtain pale yellowish oil liquid, yield 80%. 1HNMR(400MHz,CDCl 3)，δ:8.15(d,J＝1.5Hz,J＝8Hz,2H),7.50(d,2H),7.45(d,J＝8Hz,2H),7.26(d,2H),4.35(t,J＝8Hz,2H),1.95-1.85(m,2H),1.50-1.20(m,10H),0.92(t,J＝6.5Hz,3H)。
(5) synthesis of intermediate 5 (9-octyl group-3-bromine carbazole)
In 250mL single port bottle; add 9-octylcarbazol 4g (24.0mmol) successively, NBS8.5g (48.0mmol), 80mL anhydrous tetrahydro furan; under argon shield; after being heated to 80 DEG C of magnetic agitation reaction 24h, stopped reaction, reaction mixture is poured into after being cooled to room temperature in 300mL distilled water; be extracted with ethyl acetate 3 times; organic layer washes 3 times with saturated common salt again, and merge organic phase, anhydrous sodium sulfate drying spends the night.Remove solvent under reduced pressure, residue by silicagel column chromatographic separation obtains light yellow oil, productive rate 70%. 1HNMR(400MHz,CDCl 3),δ:8.21(s,1H),8.05(d,1H),7.53(d,1H),7.48(d,J＝7.2Hz,1H),7.40(d,1H),7.27(t,J＝12.0Hz,2H),4.26(t,2H),1.84(m,2H),1.25(m,10H),0.85(t,3H)。
(6) synthesis of intermediate 6 (3-(4,4,5,5-tetramethyl--1,3,2-dioxaborolanes)-9-octylcarbazol)
3-bromo-9-octylcarbazol 2g (5.6mmol) is added successively, duplex tetramethyl ethylene ketone boron ester 1.7g (6.7mmol), potassium acetate 2.7g (28mmol), Pd (dppf) Cl in 100mL there-necked flask 2150mg (0.21mmol) and 80mLDMF, vacuumizes, and under argon shield, controls oil bath temperature at 95 DEG C, magnetic agitation reaction 24h.Stopped reaction, reaction mixture is poured into after being cooled to room temperature in 200mL water, with dichloromethane extraction three times (50mL × 3), then uses saturated common salt water washing for several times, merges organic phase, anhydrous magnesium sulfate drying.Remove solvent under reduced pressure, resistates sherwood oil: ethyl acetate=20:1 is that eluent carries out silica gel (200-300 order) column chromatography for separation, obtains yellow oily liquid, productive rate 70%. 1HNMR(400MHz,CDCl 3),δ:8.60(s,1H),8.13(d,J＝7.6Hz,1H),7.92(d,J＝8.1Hz,1H),7.45(d,J＝7.3Hz,1H),7.40(t,J＝9.5Hz,2H),7.23(d,J＝7.0Hz,1H),4.30(t,J＝6.9Hz,2H),1.90-1.86(m,2H),1.44(s,12H),1.36-1.28(m,10H),0.85(t,J＝13.6Hz,3H)。
(7) synthesis of intermediate 7 (9-octyl group-2-bromine carbazole)
In 250mL there-necked flask, add 3.8g (15.4mmol) 2-bromine carbazole successively, 100mLDMSO, 0.25g (1.1mmol) TEBA and 25mL sodium hydroxide solution (50wt%), in 0.5h, 3.3g (16.9mmol) 1-bromine octane is dripped under magnetic agitation, room temperature reaction 8h, stopped reaction, add hydrochloric acid in reaction solution and regulate PH=7, be extracted with ethyl acetate (3 × 50mL), merge organic layer and use saturated common salt water washing 3 times, anhydrous magnesium sulfate drying spends the night, distilling off solvent after filtering, residuum sherwood oil is eluent column chromatography for separation, obtain yellow oily liquid, yield 65%. 1HNMR(400MHz,CDCl 3,TMS),δ:8.06(d,J＝7.2Hz,1H),7.94(d,J＝7.9Hz,1H),7.54(s,1H),7.48(t,J＝6.7Hz,1H),7.40(d,J＝7.5Hz,1H),7.33(d,J＝8.0Hz,1H),7.28–7.20(s,1H),4.24(t,J＝6.2Hz,2H),1.97–1.77(m,2H),1.35–1.25(m,10H),1.01–0.75(t,3H).
(8) synthesis of intermediate 8 (2-(4,4,5,5-tetramethyl--1,3,2-dioxaborolanes)-9-octylcarbazol)
2-bromo-9-octylcarbazol 2g (5.6mmol) is added successively, duplex tetramethyl ethylene ketone boron ester 1.7g (6.7mmol), potassium acetate 2.7g (28mmol), Pd (dppf) Cl in 100mL there-necked flask 2150mg (0.21mmol) and 80mLDMF, vacuumizes, and under argon shield, controls oil bath temperature at 95 DEG C, magnetic agitation reaction 24h.Pale yellowish oil liquid is obtained by the method for similar synthetic intermediate 6. 1HNMR(400MHz,CDCl 3,TMS),δ:8.19-8.02(m,2H),7.88(s,1H),7.69(d,J＝4.6Hz,1H),7.55–7.36(m,2H).,7.30–7.13(m,1H),4.47–4.24(m,2H),2.00–1.76(m,2H),1.50–1.30(m,12H),1.30–1.14(m,10H),0.96–0.76(t,3H).
(9) synthesis of intermediate 9 (9-(4-p-methoxy-phenyl) carbazole)
In 100mL there-necked flask, add carbazole (1.67g respectively, 10mmol), paraiodoanisole (2.57g, 11mmol), cuprous iodide (0.19g, 1mmol), salt of wormwood (2.76g, 20mmol), L-PROLINE (0.23g, 2mmol) DMSO30mL, be warming up to 90 DEG C reaction 40h.Be cooled to room temperature, thin up, extraction into ethyl acetate.Organic layer saturated common salt washes 3 times, anhydrous magnesium sulfate drying, and thick product, through silica gel column chromatography, obtains white crystal, yield 68%. 1HNMR(400MHz,CDCl 3)δ:8.14(d,J＝7.6Hz,2H),7.45–7.37(m,4H),7.33–7.24(m,4H),7.10(d,J＝8.8Hz,2H),3.90(s,3H),ppm； 13CNMR(100MHz,CDCl 3)δ:158.83,141.35,130.28,128.55,125.81,123.08,120.22,119.61,115.04,109.67,55.58.
(10) synthesis of intermediate 10 (9-(4-p-methoxy-phenyl)-3-bromine carbazole)
In 100mL single port bottle, intermediate 9 (2.71g, 10mmol) is dissolved in 30mLN; dinethylformamide, under ice-water bath condition, adds NBS (1.96g in batches; 11mmol), under argon shield, room temperature reaction spends the night; stopped reaction; reaction mixture is poured in 200mL distilled water, and with dichloromethane extraction 3 times, organic layer washes 3 times with saturated common salt again; merge organic phase, anhydrous sodium sulfate drying spends the night.Removing solvent under reduced pressure, residue by silicagel column chromatography, take sherwood oil as eluent, is separated and obtains white solid, productive rate 90%. 1HNMR(400MHz,CDCl 3)δ8.22(d,J＝21.4Hz,1H),8.08(d,J＝6.8Hz,1H),7.48–7.39(m,4H),7.33–7.27(m,2H),7.19(d,J＝7.2Hz,1H),7.11(d,J＝7.0Hz,2H),3.92(s,3H).
(11) synthesis of intermediate 11 (9-(4-p-methoxy-phenyl)-2-bromine carbazole)
2-bromine carbazole (2.45g is added successively in 100mL there-necked flask, 10mmol), paraiodoanisole (2.58g, 11mmol), cuprous iodide (190mg, 1mmol), L-PROLINE (230mg, 2mmol), salt of wormwood (2.76g, 20mmol), DMSO30mL.White crystal is obtained, productive rate 65% by the method for similar synthetic intermediate 9. 1HNMR(400MHz,CDCl 3)δ8.13(d,J＝7.1Hz,1H),8.01(d,J＝7.9Hz,1H),7.51–7.38(m,5H),7.32(d,J＝7.9Hz,2H),7.15(d,J＝7.1Hz,2H),3.95(s,3H).
(12) synthesis of intermediate 12 (3-(4,4,5,5-tetramethyl--1,3,2-dioxaborolanes)-9-(4-p-methoxy-phenyl) carbazole)
Intermediate 10 (0.65g, 1.85mmol) is added successively, duplex tetramethyl ethylene ketone boron ester (0.80g, 2.80mmol), potassium acetate (0.73g, 7.40mmol), Pd (dppf) Cl in 100mL there-necked flask 2150mg (0.21mmol) and 20mLDMF, vacuumizes, and under argon shield, controls oil bath temperature at 95 DEG C, magnetic agitation reaction 24h.White crystal is obtained, productive rate 72% by the method for similar synthetic intermediate 6. 1HNMR(400MHz,CDCl 3)δ8.25(d,J＝21.4Hz,1H),8.18(d,J＝6.8Hz,1H),7.44(dd,J＝21.1,7.8Hz,4H),7.29(dd,J＝14.5,8.6Hz,2H),7.19(d,J＝7.2Hz,1H),7.11(d,J＝7.1Hz,2H),3.92(s,3H),1.36(s,12H).
(13) synthesis of intermediate 13 (2-(4,4,5,5-tetramethyl--1,3,2-dioxaborolanes)-9-(4-p-methoxy-phenyl) carbazole)
Intermediate 11 (0.54g, 1.54mmol) is added successively, duplex tetramethyl ethylene ketone boron ester (0.57g, 2.31mmol), potassium acetate (0.59g, 6.20mmol), Pd (dppf) Cl in 100mL there-necked flask 2100mg (0.18mmol) and 20mLDMF, vacuumizes, and under argon shield, controls oil bath temperature at 95 DEG C, magnetic agitation reaction 24h.White crystal is obtained, productive rate 67% by the method for similar synthetic intermediate 6. 1HNMR(400MHz,CDCl 3)δ8.19–8.13(m,2H),7.80–7.72(m,2H),7.46(d,J＝8.7Hz,2H),7.41(d,J＝7.4Hz,1H),7.30(d,J＝8.6Hz,2H),7.13(d,J＝8.6Hz,2H),3.94(s,3H),1.36(s,12H).
(14) synthesis of intermediate 14
4-(9H-carbazole-9-base) phenylo boric acid (0.27g is added successively in the there-necked flask of 100mL, 0.94mmol), intermediate 3 (0.43g, 0.78mmol), tetra-triphenylphosphine palladium 20mg, 20mL tetrahydrofuran (THF)/toluene (V/V=1:1), salt of wormwood (1.38g, 10mmol).Vacuumize, argon shield, back flow reaction 24h at 80 DEG C.Be cooled to room temperature, thin up, dichloromethane extraction, organic phase washes 3 times, anhydrous sodium sulfate drying.Remove solvent under reduced pressure, residue by silicagel column chromatography, obtains red solid, productive rate 72%. 1HNMR(400MHz,CDCl 3)δ10.15(s,1H),8.17(d,J＝7.4Hz,2H),7.70(d,J＝7.2Hz,2H),7.52(d,J＝7.3Hz,2H),7.46(d,J＝6.5Hz,4H),7.35–7.30(m,2H),3.22–3.12(m,2H),2.83(s,3H),2.81(s,3H),2.63(s,3H),2.50(s,3H),1.84–1.66(m,2H),1.54(d,J＝4.6Hz,2H),1.47–1.40(m,2H),0.96(t,J＝6.7Hz,3H). 13CNMR(101MHz,CDCl 3)δ:186.34,158.42,149.58,140.67,137.39,131.73,128.76,127.08,126.08,125.86,123.58,120.48,120.26,119.64,116.62,109.78,109.73,32.53,31.66,28.92,22.57,15.09,14.10,14.01,13.10,12.79.
(15) synthesis of intermediate 15
In the there-necked flask of 100mL, intermediate 3 (0.24g, 0.50mmol) and intermediate 6 (0.24g, 0.60mmol) salt of wormwood (1.1g, 8.0mmol) are dissolved in the toluene of 15mL and the tetrahydrofuran (THF) of 15mL.Vacuumize, under argon shield, add tetra-triphenylphosphine palladium.Be warming up to 80 DEG C of backflows to spend the night, be cooled to room temperature, revolve and desolventize.Washed several times with water, organic phase anhydrous magnesium sulfate drying.Crude on silica gel column chromatography obtains red brown solid, productive rate 70%. 1HNMR(400MHz,CDCl 3)δ:10.14(s,1H),8.10(d,J＝7.0Hz,1H),7.91(s,1H),7.57–7.43(m,3H),7.28(d,J＝18.7Hz,2H),4.33(d,J＝6.0Hz,2H),3.21–3.07(m,2H),2.80(d,J＝10.0Hz,6H),2.56(s,3H),2.43(s,3H),1.91(d,J＝6.4Hz,2H),1.77–1.68(m,2H),1.53(d,J＝3.9Hz,2H),1.45–1.35(m,6H),1.26(s,6H),0.94(t,J＝6.0Hz,3H),0.87(s,3H). 13CNMR(101MHz,CDCl 3)δ:186.30,160.12,155.21,148.52,140.80,139.91,127.61,126.12,123.06,122.65,122.48,121.97,120.42,119.14,108.97,108.84,61.91,32.50,31.83,31.61,29.41,29.22,29.06,28.82,27.37,22.65,22.55,15.08,14.12,14.07,12.97.
(16) synthesis of intermediate 16
In the there-necked flask of 100mL, intermediate 3 (0.32g, 0.70mmol) and intermediate 8 (0.33g, 0.80mmol) salt of wormwood (1.1g, 8.0mmol) are dissolved in the toluene of 20mL and the tetrahydrofuran (THF) of 20mL.Vacuumize, under argon shield, add tetra-triphenylphosphine palladium.Be warming up to 80 DEG C of backflows to spend the night, be cooled to room temperature, revolve and desolventize.Washed several times with water, organic phase anhydrous magnesium sulfate drying.Crude on silica gel column chromatography obtains red brown solid, productive rate 70%. 1HNMR(400MHz,CDCl 3)δ:10.15(s,1H),8.19–8.08(m,2H),7.46(dd,J＝21.6,7.5Hz,2H),7.26(s,2H),7.04(d,J＝7.6Hz,1H),4.31(d,J＝12.9Hz,2H),3.14(s,2H),2.80(d,J＝9.9Hz,6H),2.57(s,3H),2.44(s,3H),1.87(d,J＝6.6Hz,2H),1.78–1.63(m,2H),1.52(d,J＝7.1Hz,2H),1.43–1.22(m,12H),0.95(t,J＝7.0Hz,3H),0.84(d,J＝6.6Hz,3H). 13CNMR(101MHz,CDCl 3) 13CNMR(101MHz,CDCl 3)δ:186.23,150.53,148.91,140.90,140.55,129.80,126.07,122.53,120.92,120.48,119.18,110.29,108.86,32.50,31.77,31.61,29.43,29.20,29.12,28.85,27.50,22.62,22.54,15.01,14.05,13.01,12.65.
(17) synthesis of intermediate 17
In the there-necked flask of 100mL, intermediate 3 (0.35g, 0.50mmol) and intermediate 12 (0.24g, 0.60mmol) salt of wormwood (1.1g, 8.0mmol) are dissolved in the toluene of 15mL and the tetrahydrofuran (THF) of 15mL.Vacuumize, under argon shield, add tetra-triphenylphosphine palladium.Be warming up to 80 DEG C of backflows to spend the night, be cooled to room temperature, revolve and desolventize.Washed several times with water, organic phase anhydrous magnesium sulfate drying.Crude on silica gel column chromatography obtains red brown solid, productive rate 70%. 1HNMR(400MHz,CDCl 3)δ10.14(s,1H),8.14(d,J＝7.6Hz,1H),7.96(s,1H),7.49(d,J＝8.6Hz,2H),7.45–7.34(m,3H),7.30(t,J＝7.3Hz,1H),7.21(d,J＝8.3Hz,1H),7.14(d,J＝8.5Hz,2H),3.94(s,3H),3.24–3.07(m,2H),2.81(s,3H),2.79(s,3H),2.57(s,3H),2.44(s,3H),1.80–1.67(m,2H),1.55–1.49(m,2H),1.45–1.40(m,2H),0.95(t,J＝7.1Hz,3H). 13CNMR(101MHz,DMSO)δ:186.29,159.08,148.64,141.78,140.87,130.02,128.55,127.90,126.39,125.85,123.70,123.40,122.77,121.89,120.34,120.07,115.21,110.01,77.39,77.07,76.75,55.67,32.51,31.63,28.84,22.56,15.07,14.07,13.00,12.61.
(18) synthesis of intermediate 18
In the there-necked flask of 100mL, intermediate 3 (0.15g, 0.50mmol) and intermediate 13 (0.24g, 0.60mmol) salt of wormwood (1.1g, 8.0mmol) are dissolved in the toluene of 15mL and the tetrahydrofuran (THF) of 15mL.Vacuumize, under argon shield, add tetra-triphenylphosphine palladium.Be warming up to 80 DEG C of backflows to spend the night, be cooled to room temperature, revolve and desolventize.Washed several times with water, organic phase anhydrous magnesium sulfate drying.Crude on silica gel column chromatography obtains red brown solid, productive rate 70%. 1HNMR(400MHz,CDCl 3)δ:10.13(s,1H),8.20(d,J＝7.9Hz,2H),7.45(dd,J＝12.6,8.3Hz,3H),7.38–7.28(m,2H),7.15–7.08(m,4H),3.91(s,3H),3.11(d,J＝5.6Hz,2H),2.80(s,3H),2.77(s,3H),2.52(s,3H),2.39(s,3H),1.77–1.61(m,2H),1.53–1.48(m,2H),1.40(dd,J＝14.3,7.1Hz,2H),0.93(t,J＝7.1Hz,3H). 13CNMR(101MHz,DMSO)δ:186.26,159.06,155.48,148.87,141.86,141.48,130.15,129.97,128.50,126.33,122.76,121.83,120.39,120.08,115.26,111.21,109.90,77.39,77.07,76.76,55.64,32.49,31.56,28.81,22.53,15.00,14.06,13.00,12.65.
Embodiment 1
(1) synthesis of Dye1:
Intermediate 14 (180mg is added successively in the there-necked flask of 100mL; 0.3mmol), cyanoacetic acid (50mg; 0.6mmol), acetonitrile (20mL), chloroform (20mL) and piperidines (0.2mL), under argon shield, 80 DEG C backflow 24h.Be cooled to room temperature, reaction solution is poured in 50mL methylene dichloride and is diluted, and washes 3 times (3 × 50mL), and the anhydrous MgSO4 of organic phase is dry.Rotary evaporation is except desolventizing, and crude on silica gel column chromatography (methylene dichloride: methyl alcohol=10:1), obtains 156mg dark red solid powder, productive rate 80%. 1HNMR(400MHz,CDCl 3)δ10.15(s,1H),8.17(d,J＝7.4Hz,2H),7.70(d,J＝7.2Hz,2H),7.51(s,2H),7.46(d,J＝6.5Hz,4H),7.32(s,2H),3.17(t,2H),2.83(s,3H),2.81(s,3H),2.63(s,3H),2.50(s,3H),1.74(s,2H),1.54(d,J＝4.6Hz,2H),1.43(d,J＝6.5Hz,2H),0.96(t,3H). 13CNMR(101MHz,CDCl 3)δ:186.34,158.42,149.58,140.67,137.39,131.73,128.76,127.08,126.08,125.86,123.58,120.48,120.26,119.64,116.62,109.78,109.73,32.53,31.66,28.92,22.57,15.09,14.10,14.01,13.10,12.79.MALDI-TOF-MS,m/z:calcdforC 39H 35BF 2N 4O 2[M] +:654.300,found:654.318.
Embodiment 2
(2) synthesis of Dye2:
150mg red-purple pressed powder is obtained, productive rate 78% by the method being similar to synthetic dyestuff 1. 1HNMR(600MHz,DMSO)δ:8.21(d,J＝7.7Hz,2H),8.12(s,1H),7.67-7.69(d,J＝7.7Hz,2H),7.62(d,J＝7.7Hz,2H),7.47(d,J＝9.8Hz,2H),7.36(d,J＝7.2Hz,2H),7.19-7.24(t,J＝7.3Hz,2H),3.12(s,2H),2.47(s,3H),2.46(s,3H),2.43(s,3H),2.41(s,3H),1.79(m,2H),1.65(m,2H),1.49(m,2H),0.90(t,J＝7.0Hz,3H). 13CNMR(151MHz,DMSO)δ:174.83,172.89,140.75,140.49,137.63,133.49,132.47,131.41,131.32,130.12,126.81,126.68,126.48,123.29,123.07,120.93,120.32,110.29,110.23,32.94,31.75,29.49,22.56,15.43,14.49,14.42,13.64,13.22.MALDI-TOF-MS,m/z:calcdforC 42H 49BF 2N 4O 2[M] +:690.400,found:690.251.
Embodiment 3
The synthesis of Dye3
145mg red-purple pressed powder is obtained, productive rate 75% by the method being similar to synthetic dyestuff 1. 1HNMR(600MHz,DMSO)δ:8.20(d,J＝6.5Hz,1H),8.17(d,J＝6.8Hz,1H),7.91(s,1H),7.60–7.55(m,2H),7.46(t,J＝7.3Hz,1H),7.21(t,J＝7.1Hz,1H),7.09(d,J＝6.7Hz,1H),4.41(s,2H),3.09(s,2H),2.48(s,6H),2.41(s,6H),1.76(s,2H),1.65(s,2H),1.48(s,2H),1.37(d,J＝6.6Hz,2H),1.23–1.13(m,10H),0.90(t,J＝6.8Hz,3H),0.78(t,J＝6.6Hz,3H). 13CNMR(151MHz,DMSO)δ:155.41,151.10,148.38,140.81,140.66,139.06,137.58,135.96,132.25,131.06,130.20,126.32,126.03,122.34,121.75,121.27,120.83,120.72,119.31,111.52,109.77,51.60,32.81,32.35,31.57,29.26,29.23,29.11,29.08,27.05,22.50,22.29,15.40,14.77,14.35,14.32,13.92,13.13.MALDI-TOF-MS,m/z:calcdforC 42H 49BF 2N 4O 2[M] +:690.400,found:690.612.
Embodiment 4
The synthesis of Dye4
160mg red solid powder is obtained, productive rate 82% by the method being similar to synthetic dyestuff 1. 1HNMR(600MHz,DMSO)δ:8.30(s,1H),8.24(s,1H),7.79(s,1H),7.59(d,J＝8.7Hz,2H),7.46(t,J＝7.7Hz,1H),7.38(t,J＝6.5Hz,2H),7.31(dd,J＝13.0,7.9Hz,2H),7.25(d,J＝8.8Hz,2H),3.90(s,3H),3.21–3.09(m,1H),2.47(s,3H),2.46(s,3H),2.44(s,3H),2.43(s,3H),1.69(dd,J＝15.7,7.8Hz,2H),1.55–1.49(m,2H),1.40(dd,J＝14.7,7.3Hz,2H),0.92(t,J＝7.3Hz,3H). 13CNMR(151MHz,DMSO)δ:166.51,162.78,159.11,155.30,148.24,141.46,140.37,138.98,137.39,132.10,130.16,129.70,128.78,126.94,126.30,124.39,123.24,122.87,120.41,119.93,119.53,115.83,112.56,110.11,110.03,109.82,109.31,55.97,33.00,32.37,31.56,22.33,15.38,14.82,14.43,14.39,13.19.MALDI-TOF-MS,m/z:calcdforC 41H 39BF 2N 4O 3[M] +:684.300,found:684.700.
Embodiment 5
The synthesis of Dye5:
148mg red brown solid powder is obtained, productive rate 78% by the method being similar to synthetic dyestuff 1. 1HNMR(600MHz,DMSO)δ:8.35(d,J＝7.9Hz,1H),8.30(d,J＝7.6Hz,1H),7.78(s,1H),7.57(d,J＝8.8Hz,2H),7.46(t,J＝7.9Hz,1H),7.32(dd,J＝16.0,7.9Hz,2H),7.22(d,J＝8.7Hz,3H),7.15(s,1H),3.87(s,3H),3.11(t,J＝10.4Hz,1H),2.44(s,3H),2.41(s,6H),2.38(s,3H),1.69–1.61(m,2H),1.49–1.45(m,2H),1.38(dd,J＝13.7,6.4Hz,2H),0.90(t,J＝7.3Hz,3H). 13CNMR(151MHz,DMSO)δ:162.63,160.84,159.03,156.18,151.35,148.58,141.52,141.13,137.77,135.55,130.84,129.97,129.60,128.68,126.90,122.73,122.53,122.30,121.12,120.50,115.87,111.45,110.10,55.92,32.34,31.41,29.50,22.28,15.46,14.77,14.37,14.26,13.89.MALDI-TOF-MS,m/z:calcdforC 41H 39BF 2N 4O 3[M] +:684.300,found:684.699.
In above-described embodiment, the related data of the ultra-violet absorption spectrum of target dyestuff Dye1 ~ 5 in dichloromethane solution and electrochemical properties is in table 1, and in embodiment, the photoelectric properties parameter of target dyestuff Dye1 ~ 5 is in table 2.
The optical physics of table 1Dye1 ~ 5 and electrochemical data
[a]InCHCl 3solutions.
[b]AbsorptionmaximumonTiO 2wasobtainedthroughmeasuringthedyesadsorbedon3μmTiO 2nanoparticlefilmsinaCHCl 3solution.
[c]E OXwasmeasuredinCH 2Cl 2andcalibratedwithferroceneasanexternalreference.
[d]E 0,0wasestimatedfromtheabsorptionthresholdsfromabsorptionspectraofdyesadsorbedontheTiO 2film.
[e]ComputedfromtheformulaE * ox＝E OX-E 0,0.
Can see that from table 1 the maximal ultraviolet absorption peak of five kinds of dyestuffs all appears at about 530nm, obvious Red Shift Phenomena has been there is compared to BODIPY mother nucleus structure (498nm), this illustrates that effective conjugate length of molecule increases, and intramolecular electronic migration strengthens.When dye molecule is adsorbed on TiO 2on film, maximal ultraviolet absorption peak all occurs that faint basket moves, and which illustrates dye molecule at nanocrystalline TiO 2deprotonation effect occurs on surface and H-assembles.The absorption spectrum of Dye4 and Dye5 is wider as seen from Figure 11, absorption intensity is larger, the carbazole which illustrating the replacement of N-phenyl is connected with BODIPY parent nucleus and creates stronger conjugative effect, effective conjugate length of molecule increases, intramolecular electronic migration strengthens, and the electron donation of D structure strengthens.Above result shows, such BODIPY dye molecule has good photon capture ability, has possessed as the necessary spectral conditions of dye sensitizing agent.Ground state oxidizing potential (the E of 5 kinds of dyestuffs can also be found out from table 1 oxvs.NHE) all than I 3-/ I -oxidation/reduction current potential (0.42Vvs.NHE) corrigendum that electricity is right, the oxidation state dye molecule namely losing electronics can effectively by I -reduction; The excited state reduction potential of dye molecule is all more negative than the energy level (-0.5Vvs.NHE) of the conduction band of titanium dioxide, the electronics of excited state just can be made effectively to be injected into the conduction band of semi-conductor, electronic circulation like this based on dye cell is fully utilized, and thus these BODIPY dyestuffs can as the sensitizing agent of titanium dioxide electrodes.
The photoelectric properties parameter of table 2Dye1 ~ 5
Five kinds of dye molecules are at AM1.5 (100mWcm -2) simulated solar irradiation under, based on the solar cell of Dye1-5 sensitization current-voltage (J-V) curve as shown in figure 13, corresponding short-circuit current (J sc), open circuit voltage (V oc), the battery parameter such as packing factor (FF) lists in table 2.The J of the solar cell device of Dye4 sensitization scfor 5.40mAcm -2, Voc is 600mV, FF value is 0.70.Make the higher reason of the battery parameter of Dye4 may be that the 3-position of carbazole ring is connected with BODIPY unit, electron-donating center, closer to by body unit, be thus more conducive to photoelectronic intramolecular migration and moves; Secondly the carbazole electron donation due to the replacement of N-p-methoxy-phenyl is stronger, and thus Dye4 has higher photoelectric current and photovoltage value.
The present invention illustrates detailed synthetic method by above-described embodiment, but the present invention is not limited to aforesaid method, does not namely mean that the present invention must rely on above-mentioned reaction conditions and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, replaces and react the change etc. of actual conditions to the equivalence of reaction solvent catalyzer of the present invention, all drops within protection scope of the present invention and open scope.

Claims (5)

1. organic dye sensitized dose of the BODIPY class of novel 2,6-positions replacements, is characterized in that having the chemical structure of general formula I:
In formula I, D is donor monomer, the one in following structural unit:
Wherein, R 1for H or alkyl or alkoxyl group;
A is by body unit, the one in following structural unit:
2. the preparation method of organic dye sensitized dose of the BODIPY class of a kind of novel 2,6-positions replacements as claimed in claim 1, is characterized in that, comprise the following steps:
(1) by 2,4-dimethyl pyrrole and acyl chlorides generation condensation reaction, then carry out complex reaction with boron trifluoride diethyl etherate, obtained intermediate 1, its structure is:
(2) intermediate 1 is through dimension David Smail formylation reaction, and obtain intermediate 2, its structure is:
(3) intermediate 2 and iodine monochloride are through electrophilic substitution reaction, obtained intermediate 3, and its structure is:
(4) carbazole and n-octane bromide are reacted under the effect of alkali, obtained intermediate 4, its structure is:
(5) intermediate 4 and N-bromo-succinimide at room temperature react, and obtain intermediate 5, its structure is:
(6) intermediate 5 and duplex tetramethyl ethylene ketone boron ester are under the catalysis of catalyzer, and through Suzuki linked reaction, obtain intermediate 6, its structure is:
(7) 2-bromine carbazole and n-octane bromide react under the effect of alkali, obtained intermediate 7, and its structure is:
(8) intermediate 7 and duplex tetramethyl ethylene ketone boric acid ester are under the catalysis of catalyzer, and through Suzuki linked reaction, obtain intermediate 8, its structure is:
(9) by paraiodoanisole and carbazole under the catalysis of catalyzer, through Liv Ullmann condensation reaction, obtained intermediate 9, its structure is:
(10) intermediate 9 and N-bromo-succinimide are reacted, obtain intermediate 10, its structure is:
(11) by paraiodoanisole and 2-bromine carbazole under the catalysis of catalyzer, through Liv Ullmann condensation reaction, obtained intermediate 11, its structure is:
(12) by intermediate 10 with duplex tetramethyl ethylene ketone boric acid ester under the catalysis of catalyzer, through Suzuki linked reaction, obtained intermediate 12, its structure is:
(13) by intermediate 11 with duplex tetramethyl ethylene ketone boric acid ester under the catalysis of catalyzer, through Suzuki linked reaction, obtained intermediate 13, its structure is:
(14) by 4-(9H-carbazole-9-base) phenylo boric acid and intermediate 3 under the catalysis of catalyzer, through Suzuki linked reaction, obtained intermediate 14, its structure is:
(15) respectively by intermediate 6,8,12,13 and intermediate 3 under the catalysis of catalyzer, through Suzuki linked reaction, obtained intermediate 15,16,17,18, its structure is:
(16) intermediate 14 ~ 18 respectively with cyanoacetic acid through Knoevenagel condensation reaction, obtained target dye molecule Dye1-5, its structure is:
3. one novel 2 as claimed in claim 2, the preparation method of organic dye sensitized dose of the BODIPY class that 6-position replaces, it is characterized in that, in step (1)-(15), the reaction medium of described reaction is one or more mixing of DMF, piperidines, tetrahydrofuran (THF), normal hexane, methylene dichloride, ethyl acetate, toluene, chloroform, ethanol.
4. one novel 2 as claimed in claim 2, the preparation method of organic dye sensitized dose of the BODIPY class that 6-position replaces, it is characterized in that, in step (6), (8), (10), (11), (12), (13), (14), (15), described catalyzer is Pd (PPh 3) 4, Pd (dppf) Cl 2, one in CuI.
5. one novel 2 as claimed in claim 2, the preparation method of organic dye sensitized dose of the BODIPY class that 6-position replaces, it is characterized in that, temperature of reaction in described step (2), (6), (8), (9), (11), (12), (13), (14), (15), (16) is 75-120 DEG C, and the reaction times of step (1)-(15) is 5-48h.
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